CN106268831B - A kind of Template synthesis Cu2O@Zn(OH)2The method of heterojunction structure - Google Patents
A kind of Template synthesis Cu2O@Zn(OH)2The method of heterojunction structure Download PDFInfo
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- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000005287 template synthesis Methods 0.000 title claims description 4
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002105 nanoparticle Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000010949 copper Substances 0.000 claims description 56
- 239000000725 suspension Substances 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 29
- 238000002360 preparation method Methods 0.000 abstract description 12
- 239000002086 nanomaterial Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 abstract 1
- 235000019345 sodium thiosulphate Nutrition 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 12
- 229960000907 methylthioninium chloride Drugs 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 10
- 238000007146 photocatalysis Methods 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000005291 magnetic effect Effects 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 241000167854 Bourreria succulenta Species 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 235000019693 cherries Nutrition 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000004776 molecular orbital Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000736199 Paeonia Species 0.000 description 1
- 235000006484 Paeonia officinalis Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/26—Organic substances containing nitrogen or phosphorus
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
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- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- General Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Catalysts (AREA)
Abstract
It is open to describe a kind of simple template method synthesis Cu the present invention relates to field of nano material preparation2O@Zn(OH)2The preparation method of heterojunction structure nano material.Synthesize to obtain three kinds of patterns with water bath Method first uniform, stable structure, Cu of the size in 1 μm or so of regular octahedron2O nano particle, using it as template, be added sodium thiosulfate after with Cu2O reacts, while in Cu2The outer surface of O produces hydroxide ion, and liquor zinci chloridi is then added, Zn will occur at this time2+With OH‑Reaction in Cu2The outer surface of O forms Zn (OH)2Nanometer sheet finally passes through centrifugal drying, has just obtained Cu2O@Zn(OH)2Heterojunction structure.The heterojunction material that the present invention synthesizes has the pattern of stable homogeneous, large specific surface area, and has fabulous catalytic performance, high recycling rate.The present invention is a kind of novelty, only one preparation Cu2O@Zn(OH)2The method of hetero-junctions.
Description
Technical field
The preparation method for the nano material that the present invention refers to, especially simple chemical template method synthesis large specific surface area
Cu2O@Zn(OH)2The method of nano heterojunction.
Background technique
Nano material and nanostructure are as one of 21 century most important new material, because it is with unique physical property
And chemical property, it is all applied in many fields, the development of future society economy, technology is suffered from and greatly facilitates work
With, be promote progress of human society important force.Nano material refers to nanometer powder or nanometer powder by a series of systems
Thin-film material or block materials obtained from standby technique, due to being increased considerably with nano material number of grain boundaries, so that material
Intensity, toughness and superplasticity greatly improve.This is just to the electricity of material, magnetics, mechanics, and the performances such as optics generate important shadow
It rings.After nano-scale declines to a certain extent, electron energy level is changed into discrete energy by quasi-continuous near metal ion Fermi surface
Grade；And molecular orbital energy level and the minimum molecular orbital energy not being occupied that highest existing for Nano semiconductor particle is occupied
Grade, so that the phenomenon that energy gap band broadens, the referred to as quantum size effect of nanoparticle.This variation is to the various of nanoparticle
Performance all produces very big influence, produces the light completely different with conventional material, electricity, heat, chemistry or mechanical property.Nanometer
The target in technology future is that as required, manipulation atom, molecule construction nanoscale have the device or product of certain function.
Cu2The one kind of O as semiconductor nano material, its price is excellent, and has excellent characteristic, Cu2O conduct
P-type semiconductor, forbidden bandwidth 2.17eV are widely used in terms of hydrogen manufacturing, superconductor, solar battery and photocatalysis at present.
For in the present invention, we have prepared the different Cu of pattern2O nano particle causes to expose different because of the difference of its pattern
Active face, the different of active face have a significant impact to catalytic performance tool, and Cu2O is as excellent visible light catalyst, storage
It measures big, nontoxic cheap.But still photo-generated carrier it is unstable, be easy the defects of compound, thus substantially reduce its photocatalysis
Efficiency.By template in Cu2The outer surface of O introduces one layer of Zn (OH)2, these Zn (OH)2Nanometer sheet is conducive to photo-generated carrier
Transfer, and then lead to the separation of hole-electron, photo-catalysis capability is strengthened, so preparation Cu2O/Zn(OH)2Hetero-junctions
The nano material of structure can obviously overcome Cu2O defect possessed by photocatalysis field reaches the effect of enhancing catalytic efficiency
Fruit.
Summary of the invention
In order to overcome Cu2Defect of the O as nano-photocatalyst material, the object of the invention is to be to provide a kind of nanometer
The preparation method of heterojunction structure prepares a kind of Cu2O nano particle and Zn (OH)2The nano-photo catalytic of the heterojunction structure of nanometer sheet
Material, to improve the photocatalysis performance of material entirety.
In order to reach above-mentioned purpose, the step process of the technical solution adopted by the present invention is as follows: a kind of Template synthesis
Cu2O@Zn(OH)2The method of heterojunction structure, includes the following steps:
(1) it disperses 8.8g polyvinylpyrrolidone in the deionized water of 100ml, adds 0.172g copper chloride, stir
It mixes uniformly, forms nattier blue solution, then heat to 55 degrees Celsius；
(2) the NaOH aqueous solution that 10ml concentration is 2mol/L is added dropwise, after 30min, then is added dropwise into flask
10ml concentration is the aqueous ascorbic acid of 0.6mol/L, is finally maintained under 55 C water baths and is stirred to react 3 hours, finally
Obtain wine-colored suspension；
(3) suspension that reaction obtains in step (2) is terminated into reaction, centrifugation through 8000rpm/min centrifuge separation 8min
Mixed liquor (volume ratio of the mixed liquor of water and dehydrated alcohol is 1:1) centrifuge washing of product water and dehydrated alcohol, obtains just
Cu octahedronlike2O nano particle, the Cu2O particle exposes { 111 } active face of 8 wholes.
(4) by Cu obtained in step (3)2After O nano particle is dry, 0.02g is weighed, 15ml deionized water is scattered in
In the mixed solution of 15ml dehydrated alcohol composition, red suspension is obtained, then by suspension ultrasonic Separation 15min, ultrasound
Power is 250W, obtains finely dispersed suspension；Suspension is heated to 40 degrees Celsius under agitation；
(5) Na that 6ml concentration is 1mol/L is added in beaker in (4)2S2O3·5H2O aqueous solution, it is anti-under 40 degrees Celsius
Pink suspension is obtained after answering 15min, adds the ZnCl that 2ml concentration is 0.12mol/L2Aqueous solution reacts 5min,
Suspension at this time is arrived into Cu by 8000rpm/min centrifuge separation 8min again2O@Zn(OH)2, followed in turn by water and nothing
Mixed liquor (mixeding liquid volume of water and dehydrated alcohol ratio is 2:1) centrifuge washing of water-ethanol, finally obtains regular octahedron shape
Cu2O@Zn(OH)2Hetero-junctions.
The present invention has the advantage that aspect is:
(1) reaction carries out in the liquid phase and prepares material by chemically reacting, and preparation method is simple, repeats system
Standby, products pure is nontoxic.
(2) preparation process only carries out in deionized water or deionized water-alcohol blend, raw materials used simple, price
Cheaply, products therefrom is uniform, stablizes, and will not have an adverse effect to environment.
(3) for the present invention first by the dosage of regulation polyvinylpyrrolidone (PVP), the reaction time has obtained size 1
μm or so Cu2O crystal grain, stable appearance is of uniform size, and 6 { 111 } high activity faces of exposure, further prepares
Cu2O@Zn(OH)2, 560nm or so is reached to the absorbing wavelength of sunlight, has had reached the absorption application to visible light,
In the hetero-junctions, due to Cu2The exposure of O active face has a significant impact to catalytic activity, Zn (OH)2Nanometer sheet there are further
Strengthen the catalytic activity of material.It is tested by the experiment of photocatalysis methylene blue (MB), after the degradation time of 150min, drop
Solution ability has reached 98.6%.The material that the present invention is prepared is sensed in medicine, and sterilization, photocatalysis field has well
Using.
Detailed description of the invention
Fig. 1 is the pure Cu of the three kinds of patterns prepared2O nanostructure is cube (Figure 1A), cuboctahedron (figure respectively
1B) and the scanning electron microscopic picture of regular octahedron (Fig. 1 C).
Fig. 2 is the three kinds of pattern Cu prepared2The XRD characterization effect picture of O nano material, the Cu of regular octahedron shape2O (A) is stood
Side Cu octahedronlike2O (B), the Cu of cubic2O(C)。
Fig. 3 is that prepare is the Cu of three kinds of patterns2O forms Zn (OH) on respective surface2The Cu of lamella2O@Zn(OH)2It is different
The scanning electron microscopic picture of the material of matter structure, figure A are the Cu of cubic2O@Zn(OH)2The low power figure of hetero-junctions schemes A1It is vertical
The Cu of cube shape2O@Zn(OH)2The high power figure of hetero-junctions；Figure B is the Cu of cuboctahedron shape2O@Zn(OH)2The low power of hetero-junctions
Figure schemes B1It is the Cu of cuboctahedron shape2O@Zn(OH)2The high power figure of hetero-junctions；Figure C is the Cu of regular octahedron shape2O@Zn
(OH)2The low power figure of hetero-junctions schemes C1It is the Cu of regular octahedron shape2O@Zn(OH)2The high power figure of hetero-junctions.
Fig. 4 is the Cu of the three kinds of patterns prepared2O@Zn(OH)2The ultraviolet-ray visible absorbing map of hetero-junctions, A are cubes
The Cu of shape2O@Zn(OH)2The ultraviolet-ray visible absorbing figure of hetero-junctions；B is the Cu of cuboctahedron shape2O@Zn(OH)2Hetero-junctions
Ultraviolet-ray visible absorbing figure；C is the Cu of regular octahedron shape2O@Zn(OH)2The ultraviolet-ray visible absorbing figure of hetero-junctions.
Fig. 5 is the cube Cu prepared2O@Zn(OH)2The effect picture of the degradation MB of hetero-junctions.
Fig. 6 is the cuboctahedron Cu prepared2O@Zn(OH)2The effect picture of the degradation MB of hetero-junctions.
Fig. 7 is the regular octahedron Cu prepared2O@Zn(OH)2The effect picture of the degradation MB of hetero-junctions.
Specific embodiment
Embodiment 1:
It is carried out according to the step of technical solution.Firstly, the round bottom that 0.55g polyvinylpyrrolidone is added to 250ml is burnt
In bottle, the deionized water of 100ml is added, 0.172g copper chloride is being separately added into flask, then in C-MAG
It is uniformly mixed to form nattier blue solution under HS7IKAMAG type heating magnetic stirring apparatus, and it is Celsius to heat to 55
Degree the NaOH aqueous solution 10ml that concentration is 2mol/L is added dropwise into round-bottomed flask, at this moment solution is by light after temperature is stablized
Blue is converted to black, after reacting 30min, then the aqueous ascorbic acid that concentration is 0.6mol/L is added dropwise into flask
10ml, forms cherry microemulsion afterwards, is finally maintained at after stirring water-bath 3 hours under 55 degrees Celsius, finally obtains peony
Suspension.After reaction, suspension reaction obtained is centrifugated by 8000rpm/min CTK80 type centrifuge
8min reacts its termination, and the mixed liquor of the product obtained in this way water and dehydrated alcohol is centrifuged back and forth by CTK80 centrifuge
Washing, obtains the pure cube Cu having a size of 1 μm or so2O nano particle, the Cu2O particle exposes 6 { 100 } active faces,
As shown in Figure 1A and Fig. 2A.Cu obtained in then will be above-mentioned2O nano particle is dried in vacuo 3 hours dry at 60 c
Afterwards, it weighs 0.02g to be put into 100ml beaker, 15ml deionized water next is added in beaker and 15ml dehydrated alcohol obtains
Suspension ultrasonic Separation 15min, ultrasonic power 250W are then obtained finely dispersed suspension, then by red suspension
It is stirred in the case where C-MAG HS7IKAMAG type heats magnetic apparatus, and heats to 40 degrees Celsius, to beaker after temperature is stable
It is middle that the Na that concentration is 1mol/L is added2S2O3·5H2O aqueous solution 6ml, react under 40 degrees Celsius obtain after 15min it is pink
Suspension adds the ZnCl that concentration is 0.12mol/L2Aqueous solution 2ml reacts 5min, then suspension at this time is passed through
8000rpm/min CTK80 centrifuge is centrifugated 8min to get desired product Cu is arrived2O@Zn(OH)2, followed in turn by water with
The mixed liquor of dehydrated alcohol centrifuge washing back and forth, finally obtains the Cu of pure cubic2O@Zn(OH)2Hetero-junctions is such as schemed
Shown in the scanning electron microscope of 3A and A1；The dissimilar materials can be seen that the analysis of element contained by material by its energy spectrum diagram (EDS)
It is made of Cu, Zn, O and H, in conjunction with ftir analysis instrument (FT-IR) it can be found that the material exists
3239cm-1And 1626cm-1There is stronger absorption peak wherein 3239cm at two-1The absorption peak at place is the stretching vibration frequency of hydroxyl
Rate illustrates to generate Zn (OH) in product2, and it is located at 1626cm-1The absorption peak at place is O-H bond bending vibration absorption peak；This two
A peak all demonstrates depositing for hydroxyl；The combination of two characterizations, the hetero-junctions for also demonstrating preparation is by Cu2O and Zn (OH)2Composition.
Embodiment 2:
It is carried out according to the step of technical solution.Firstly, 3.3g polyvinylpyrrolidone to be added to the round-bottomed flask of 250ml
In, the deionized water of 100ml is added, 0.172g copper chloride is being separately added into flask, then in C-MAG HS7IKAMAG
It is uniformly mixed to form nattier blue solution under type heating magnetic stirring apparatus, and heats to 55 degrees Celsius, to temperature
After stabilization, the NaOH aqueous solution 10ml that concentration is 2mol/L is added dropwise into round-bottomed flask, at this moment solution is by light blue conversion
For black, after reacting 30min, then the aqueous ascorbic acid 10ml that concentration is 0.6mol/L, rear shape are added dropwise into flask
At cherry microemulsion, finally it is maintained at after being stirred water-bath 3 hours under 55 degrees Celsius, finally obtains wine-colored suspension.
After reaction, the suspension that reaction obtains is made into its end by 8000rpm/min CTK80 type centrifuge centrifuge separation 8min
It only reacts, the mixed liquor of the product water and dehydrated alcohol that obtain in this way passes through CTK80 centrifuge centrifuge washing back and forth, obtains ruler
The Cu of the very little pure cuboctahedron shape for being 1 μm or so2O nano particle, the Cu2O particle exposes 6 { 100 } active faces and 12
{ 111 } face of a high activity, as shown in fig. ib and fig. 2b.Cu obtained in then will be above-mentioned2O nano particle is at 60 c
After dry 3 hours of vacuum drying, weigh 0.02g and be put into 100ml beaker, be next added in beaker 15ml deionized water and
15ml dehydrated alcohol obtains red suspension, is then dispersed suspension ultrasonic Separation 15min, ultrasonic power 250W
Uniform suspension then stirs in the case where C-MAG HS7IKAMAG type heats magnetic apparatus, and heats to 40 degrees Celsius,
The Na that concentration is 1mol/L is added into beaker after stablizing for temperature2S2O3·5H2O aqueous solution 6ml reacts under 40 degrees Celsius
Pink suspension is obtained after 15min, adds the ZnCl that concentration is 0.12mol/L2Aqueous solution 2ml reacts 5min, then will
Suspension at this time arrives desired product Cu by 8000rpm/min CTK80 centrifuge centrifuge separation 8min2O@Zn
(OH)2, followed in turn by the mixed liquor of water and dehydrated alcohol centrifuge washing back and forth, finally obtain pure cuboctahedron shape
Cu2O@Zn(OH)2Hetero-junctions, as shown in the scanning electron microscope of Fig. 3 B and B1；By its energy spectrum diagram (EDS) to element contained by material
Analysis is it can be seen that the dissimilar materials is made of Cu, Zn, O and H, in conjunction with ftir analysis instrument (FT-
IR) it can be found that the material is in 3239cm-1And 1626cm-1There is stronger absorption peak wherein 3239cm at two-1The absorption peak at place
It is the stretching vibration frequency of hydroxyl, illustrates to generate Zn (OH) in product2, and it is located at 1626cm-1The absorption peak at place is that O-H key is curved
Bent vibration absorption peak；The two peaks all demonstrate depositing for hydroxyl；Two characterization combinations, also demonstrate preparation hetero-junctions be by
Cu2O and Zn (OH)2Composition.
Embodiment 3:
It is carried out according to the step of technical solution.Firstly, 8.8g polyvinylpyrrolidone to be added to the round-bottomed flask of 250ml
In, the deionized water of 100ml is added, 0.172g copper chloride is being separately added into flask, then in C-MAG HS7IKAMAG
It is uniformly mixed to form nattier blue solution under type heating magnetic stirring apparatus, and heats to 55 degrees Celsius, to temperature
After stabilization, the NaOH aqueous solution 10ml that concentration is 2mol/L is added dropwise into round-bottomed flask, at this moment solution is by light blue conversion
For black, after reacting 30min, then the aqueous ascorbic acid 10ml that concentration is 0.6mol/L, rear shape are added dropwise into flask
At cherry microemulsion, finally it is maintained at after being stirred water-bath 3 hours under 55 degrees Celsius, finally obtains wine-colored suspension.
After reaction, the suspension that reaction obtains is made into its end by 8000rpm/min CTK80 type centrifuge centrifuge separation 8min
It only reacts, the mixed liquor of the product water and dehydrated alcohol that obtain in this way passes through CTK80 centrifuge centrifuge washing back and forth, obtains
Cu having a size of 1 μm or so of pure regular octahedron shape2O nano particle, the Cu2The exposure of O particle is that 8 activity are high
{ 111 } face, as shown in figures 1C and 2C.Cu obtained in then will be above-mentioned2O nano particle is dried in vacuo dry at 60 c
It after dry 3 hours, weighs 0.02g and is put into 100ml beaker, 15ml deionized water and the anhydrous second of 15ml are next added in beaker
Alcohol obtains red suspension, and suspension ultrasonic Separation 15min, ultrasonic power 250W are then obtained finely dispersed suspension
Liquid then stirs in the case where C-MAG HS7IKAMAG type heats magnetic apparatus, and heats to 40 degrees Celsius, after temperature is stablized
The Na that concentration is 1mol/L is added into beaker2S2O3·5H2O aqueous solution 6ml, react under 40 degrees Celsius obtain after 15min it is light
Red suspension adds the ZnCl that concentration is 0.12mol/L2Aqueous solution 2ml reacts 5min, then by suspension at this time
8min is centrifugated by 8000rpm/min CTK80 centrifuge to get desired product Cu is arrived2O@Zn(OH)2, followed in turn by
The mixed liquor of water and dehydrated alcohol centrifuge washing back and forth, finally obtains the Cu of pure positive eight bodies shape2O@Zn(OH)2Hetero-junctions, such as
Shown in the scanning electron microscope of Fig. 3 C and C1；The heterogeneous material can be seen that the analysis of element contained by material by its energy spectrum diagram (EDS)
Material is made of Cu, Zn, O and H, in conjunction with ftir analysis instrument (FT-IR) it can be found that the material exists
3239cm-1And 1626cm-1There is stronger absorption peak wherein 3239cm at two-1The absorption peak at place is the stretching vibration frequency of hydroxyl
Rate illustrates to generate Zn (OH) in product2, and it is located at 1626cm-1The absorption peak at place is O-H bond bending vibration absorption peak；This two
A peak all demonstrates depositing for hydroxyl；The combination of two characterizations, the hetero-junctions for also demonstrating preparation is by Cu2O and Zn (OH)2Composition.
The pure Cu that the first step of preparation process obtains2O nano particle, by regulating and controlling the difference of polyvinylpyrrolidone (PVP) dosage, instead
Lengthening between seasonable, has obtained crystal grain of the size at 1 μm or so, the Cu that the present invention obtains2O crystal is very big in size
Can also ensure stable appearance simultaneously, size it is uniform, this be it is especially rare, also to provide guarantor with good catalytic performance
Barrier.In addition, the Cu of three kinds of patterns2O particle exposes different active faces, the Cu for the cubic that embodiment 1 is prepared2O is sudden and violent
Dew is 6 { 100 } active faces, the cuboctahedron Cu that embodiment 2 is prepared2O exposure be 6 { 100 } active faces and
{ 111 } face of 12 high activities, and the regular octahedron Cu that embodiment 3 is prepared2O exposure is entirely 6 { 111 } high living
Property face, wherein since the activity in { 111 } face is higher than { 100 } face, so catalytic activity most preferably positive eight in three kinds of initial patterns
The Cu of face body shape2O nano particle.The Cu that second step is prepared2O@Zn(OH)2Nano particle reaches the absorbing wavelength of sunlight
560nm or so, has had reached the absorption application to visible light, in the hetero-junctions, due to Cu2The exposure of O active face is to catalysis
Activity has a significant impact, Zn (OH)2The presence of nanometer sheet further enhances the catalytic activity of material.This sound to visible light
It answers, facilitates application of the material to solar energy, the material being prepared is sensed in medicine, and sterilization, photocatalysis field has very well
Application.
It is tested by the experiment of photocatalysis methylene blue (MB), detailed process is to weigh 5mgCu2O@Zn(OH)2Particle adds
Enter to 40mL, in the MB solution of 20mg/L, then by suspension magnetic stirring apparatus uniform stirring, and is handled under dark situation
30min balances to reach the absorption-desorption between catalyst and MB, then by the xenon lamp (CEL-HXF300Beijing of 300W
Aulight Co., Ltd, China have a ultraviolet filter, the available visible light greater than 400nm) it is placed on from outstanding
Start illumination at supernatant liquid 10cm, illumination period suspension will continue to stir, and maintain reaction system under the protection of condensation cycle water
The equalized temperature of system takes a sample every 30min, catalysis reaction is terminated after 150min, is analyzed finally by U-3900UV-vis
The absorption peak strength of MB after instrument measurement catalysis, test result is as illustrated in figs. 5-7.The result shows that the Cu of regular octahedron shape2O@Zn
(OH)2Either compared to pure Cu2O nano particle or cubic or cuboctahedron shape Cu2O@Zn(OH)2It is heterogeneous
Knot, that the former exposes is high activity { 111 } face and Zn (OH) entirely2The presence of nanometer sheet also has the transfer of electronics very big
Help, so further promoting the ability of the photocatalytic degradation MB of material, after the degradation time of 150min, degradation capability
Reach 98.6%.The Cu for the regular octahedron shape that we construct in summary2O@Zn(OH)2The light of MB is urged in constructing for hetero-junctions
Changing degradation has the effect of fabulous, therefore material has very big application future in photocatalysis field.
Claims (1)
1. a kind of Template synthesis Cu2O@Zn(OH)2The method of heterojunction structure, which comprises the steps of:
(1) it disperses 8.8g polyvinylpyrrolidone in the deionized water of 100ml, adds 0.172g copper chloride, stirring is equal
It is even, then heat to 55 degrees Celsius；
(2) 10ml concentration is added dropwise as the NaOH aqueous solution of 2mol/L, after 30min, then 10ml concentration is added dropwise and is
The aqueous ascorbic acid of 0.6mol/L is finally maintained under 55 C water baths and is stirred to react 3 hours, finally obtains suspension
Liquid；
(3) suspension that reaction obtains in step (2) is terminated into reaction through 8000rpm- centrifuge separation 8min, centrifugation product is used
The mixed liquor centrifuge washing of water and dehydrated alcohol obtains regular octahedron shape Cu2O nano particle, the Cu2O particle exposes 8 entirely
{ 111 } active face in portion；Wherein, in the mixed liquor of water and dehydrated alcohol, the volume ratio of water and dehydrated alcohol is 1:1；
(4) by Cu obtained in step (3)2After O nano particle is dry, 0.02g is weighed, 15ml deionized water and 15ml are scattered in
In the mixed solution of dehydrated alcohol composition, red suspension is obtained, then by suspension ultrasonic Separation 15min, ultrasonic power is
250W obtains finely dispersed suspension；Suspension is heated to 40 degrees Celsius under agitation；
(5) Na that 6ml concentration is 1mol/L is added in the suspension prepared to step (4)2S2O3·5H2O aqueous solution, 40 degrees Celsius
After lower reaction 15min, the ZnCl that 2ml concentration is 0.12mol/L is added2Aqueous solution reacts 5min, then by suspension at this time
8min is centrifugated by 8000rpm/min to get Cu is arrived2O@Zn(OH)2, followed in turn by the mixed liquor of water and dehydrated alcohol from
Heart washing, finally obtains the Cu of regular octahedron shape2O@Zn(OH)2Hetero-junctions；Wherein, in the mixed liquor of water and dehydrated alcohol, water with
The volume ratio of dehydrated alcohol is 2:1.
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| CN104327574A (en) * | 2014-09-29 | 2015-02-04 | 中国海洋大学 | Micro/nano Cu2O/ZnO composite material, preparation method and application thereof |
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| CN104327574A (en) * | 2014-09-29 | 2015-02-04 | 中国海洋大学 | Micro/nano Cu2O/ZnO composite material, preparation method and application thereof |
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